Photographic developer containing substituted sulfonamide groups



Patented Aug. 28,

PHoToGRAPnic iJEvELoi iin. commits. SUBSTITUTED SULFONAMIDET GROUPS Arnold Weissberger and Dudley B. Glass, Rochester, N. Y., assignors to Eastman Kodak Com- .pany, Rochester, N. Y., a corporation of New Jersey N0 Drawing. Application. 23, 1947, Serial No. 750,178

3 Claims. 1

This invention relates to photographic developers and more particularly to photographic developers containing N-substituted sulfonamide groups.

It is known that photographic developers of the p-phenylenediamine type are valuable compounds for producing fine grain black and white photographic images and also that these compounds, especially when they contain alkyl substituents on one of the nitrogen atoms are useful as developers in producing colored photographic images. A serious disadvantage of the p-phenylenediamine developers is that they are highly allergenic, that is, they are poisonous to the human skin and therefore are dangerous to use.

The allergenic properties of the p-phenylenediamine developers may be overcome by substituting a sulfonamide group or amino sulfonyl group in the alkyl group on the nitrogen atom of p-phenylenediamine as described in Weissberger U. S. Patent 2,193,015, granted March 12, 1940. The dyes produced from these developing agents by coupling are, however, sometimes too soluble and therefore are of low density when used as photographic images.

It is therefore an object of the present invention to provide a new class of photographic developing agents of the p-phenylenediamine type. A further object is to provide developing agents of the p-phenylenediamine type which produce dye images having the desired solubility characteristics.

These objects are accomplished by the present invention by the use as developing agents of compounds of the following general formulas:

CHzCHzN-SOzR where R, R, R' and R' represent alkyl groups especially lower alkyl groups and X represents hydrogen, a lower alkyl group or a lower alkoxy r up.

By lower alkyl group and lower allbxy group, We mean a methyl or niethoizy group, ethyl or ethoxy group, propyl or propoxy group andbutylorbutoxygroup. o r

5 Compounds of this class which may be used according to our invention are as follows:

. 9 1. can onzonm soiom NH2 i V l-amino N-ethyl-N- (N'-niethyl-B-methylsulfonamidoethyl aniline 2 CzH CHzCHz-N-AOzCHs 4-a1nino-N-ethyl-N(N-methy1B-lnethylsulfoiliiinidotliyl) 3-methylaniline 4-amino-N,N-diethy1-3- N -methy1-/3-methylsulfonamidoethyD-aniline These compounds were prepared as follows:

1. 4-amino-N-ethyl-N-(N methyl-p-methylsulfonamidoethyl) -aniline was prepared from N- ethylaniline by the following series of reactions:

at. N-p-aminoethyZ-N-ethyZaniline.A mixture of N-ethylaniline (2.0 mols) and ,B-bromoethylamine hydrobromide (1.0 mol) was placed in a flask in an oil bath and the temperature of the oil bath was raised to 145-150 C. during 45 minutes. The reaction mixture was stirred at this temperature for 2 hours, cooled, diluted with water, and made alkaline with 40 per cent sodium hydroxide solution. The amine was extracted with ether, the ethereal solution was washed with water and the ether was evaporated. The residue was distilled under reduced pressure, collecting the fraction that boiled at l20-122/6 mm.

. b. N-ethyZ-Ne(p-methyZsuljonamidoethyl)ani- Zzne.Nflaminoethyl-N ethylaniline (1.0 mol) was mixed with water'(l l.) and'stirred vigorously at 20 C. while methanesulfonyl chloride (1.0 mol) was dropped in during the course of 30 minutes. After each quarter of the methanesulfonyl chloride had been added, one-quarter of a solution of 40 g. of sodium hydroxide in 200 ml. of water was added. The reaction mixture was stirred for 45 minutes and the amide was extracted with chloroform. The chloroform solution Was dried over anhydrous sodium sulfate and the chloroform was evaporated under reduced pressure. The residue was the desired product.

c. N ethyl-N-(N'-met yZ-/3-mcthylsulfovuamridoethyl) aniZine.-N-ethy1 N-(p methylsulfonamidoethyDaniline (0.5 mol) Was dissolved in 1 l. of water which contained 50 g. of sodium hydroxide. The temperature was maintained at 35 C. and methyl sulfate (0.6 mol) was dropped in with stirring, during a period of 20 minutes. The reaction mixture was stirred at 25-30 for 2 hours and the amide was extracted with ether or chloroform. The solution was washed with water, dried over anhydrou sodium sulfate and the solvent was removed under reduced pressure.

The product was an oil.

d. N -cthyZ-N (N -methyl-p-methylsuljonamidoethyl) 4 nitrosoaniline-N ethyl N (N methyl-p-methylsulfonamidoethyl) -aniline (0.2 mol) was dissolved in a solution of 200 ml. of water and 50 ml. of concentrated hydrochloric acid, and nitrosated at C. by the addition of 14 g. of sodium nitrate dissolved in 60 ml. of water. After standing for -30 minutes, the reaction mixture was made alkaline with ammonium hydroxide. The product was separated from the alkaline solution and crystallized from alcohol.

e. 4 amino N ethyl N(N methyl p methylsulfonamidoethyl) am'Ziner-N ethyl N (N' methyl fi methylsulfonamidoethyl) 4 nitrosoaniline (0.1 mol) was dissolved in 150 ml. of absolute alcohol and reduced in the presence of Raney nickel at a temperature of 60 C. and a hydrogen pressure of 45 lbs/in. lhe catalyst was removed by filtration and the product was converted to the sulfate by the addition of 5.6 ml. of concentrated sulfuric acid dissolved in 20 ml. of absolute alcohol. After standing at 0 C. for days, the product had crystallized. The precipitate was filtered off, washed with absolute alcohol and dried in a vacuum desiccator.

2. 4 amino N ethyl N (N' methyl p methylsulfonamidoethyl) 3 methylaniline was prepared from N-ethyl-m-toluidine by the same procedures as used for the preparation of 4-ami- .qhydroxide solution.

no N ethyl N (N methyl p methylsulfonamidoethyl) -aniline (compound 1).

3. 4 amino -N- ethyl- N (N ethyl -,B methylsulfonamidoethyl)-3-methylaniline was prepared from N-ethyl-m-toluidine by the same procedure as used for the preparation of compound 1 except that ethyl sulfate instead of methyl sulfate was used to introduce the alkyl group into the methylsulfonamide compound.

4. 4 amino N ethyl N (N methyl 5 methylsulfonamidoethyl) m phenetidine was prepared from N-ethyl-m-phenetidine by the same procedure used for the preparation of compound 1;

5. 4 amino N,N diethyl 3 (N methyl ,8-methylsulfonamidoethyl) -aniline was prepared in the following manner.

a. m-if\lz'trobenzyl bromide. -MNitrotoluene .(5 mols) was heated at 135:59 and bromine (5 mols) was dropped in during a period of 5 hours. During this time the reaction mixture was exposed to the light of a 200 w. clear bulb. The reaction mixture was cooled, dissolved in ether and the ether was dried over anhydrous sodium sulfate. The ether was evaporated and the residue was distilled under reduced pressure collecting the fraction that boiled at l20-150/2 mm. This crude product was redistilled under reduced pressure collecting the portion that boiled at 160- l62f/14 mm. This redistilled material was recrystallized from methanol and dried in air. Melting point 58-59".

b. m-NitrophenylacetonitriZe.-Sodium cya. nide (1.0 mol) was dissolved in ml. of water. Alcohol (280 ml.) was added and the mixture was cooled to 20 C. m-Nitrobenzyl bromide (0.8 mol) was added and the reaction mixture was stirred and warmed slowly to 40 C. At this temperature the heating was stopped and the exothermic allowed to proceed. The. temperature was not allowed to rise above 60-65".

After the spontaneous reaction was over, the reaction mixture was boiled for 1 hour. The alcohol was removed under reduced pressure and the residue was dissolved in 250 ml. water plus 300 ml. of ether. The layers were separated, and the ether layer was washed with Water and dried over anhydrous sodium sulfate. The ether was evaporated and the residue was distilled under reduced pressure collecting the fraction that boiled at l60-165/3 mm. The product was recrystallized from methanol. Melting point 61- 62.

c. Aminophenylacetonitrile.m-Nitrophenylacetonitrile (0.9 mol) was added to a solution of stannous chloride (2.7 mols) in concentrated hydrochloric acid (700 ml.). The temperature of the reaction mixture was maintained at 35- 40", by cooling, until the exothermic reaction subsided. After stirring for 2 hours, the solution was made alkaline with 2 l. of 40 per cent sodium This mixture was diluted with 1 l. of water and the product extracted with ether. The ethereal solution was washed with water, dried over anhydrous sodium sulfate and the ether was evaporated. The residue was distilled under reduced pressure collecting the portion that boiled at 132-135/2 mm.

d. m- (N,N'-dz'ethylamino) phenylacetonitrite.- A mixture of m-aminophenylacetonitrite (0.75 mol), alcohol (400 ml.), sodium carbonate (1.0 mol) water ml.) and ethyl iodide (1.8 mols) was boiled under reflex for 6 hours. The alcohol was removed under reduced pressure and the residue was dissolved in a mixture of water (500 ml.) and ether (500 ml.). The ether layer was separated, washed with water and dried over anhydrous sodium sulfate. The ether was evaporated and the residue was distilled under reduced pressure collecting the fraction that boiled at 125-130/2 mm.

e. m (,9 Aminoethyl) N,N diethyZaniZine.- m- (N,N-diethylamino) -phenylacetonitrile (0.66 mol) was placed in a high pressure reduction apparatus with liquid ammonia (250 ml.) and methanol (150 ml.) and hydrogenated at 110 C. in the presence of Fancy nickel g.) and a hydrogen pressure of 1500 lbs/in. The product was distilled under reduced pressure collecting the fraction that boiled at 148-150 /10 mm.

f. 4 amino N,N diethyl 3 (N' methyl B-methylsulfonamidoethyl) -aniline was prepared from m- (p-aminoethyl) -N,N-diethylaniline by the same procedures used to convert N-(fi-aminoethyl) -N-ethylaniline into compound 1.

When used for the formation of colored photographic images, the developers of our invention may be used in conjunction with any well-known coupler compound such as those described in Fischer 1,102,028, granted June 30, 1914; Mannes and Godowsky U. S. Patent 2,108,602, granted February 15, 1938; or Mannes, Godowsky and Peterson 2,115,394, granted April 26, 1938, and 2,126,337, granted August 9, 1938.

The following example illustrates a developing solution which may be used according to our invention.

Gms. 4-amino-N-ethyl-N- (N' -methyl 3-methylsulfonamido)ani1ine 1 Sodium sulfite 0.5 Sodium carbonate 20 Potassium bromide 1 Water to 1 liter Coupler (o-chlorophenylphenol) gms 2 Sodium hydroxide (10% solution) cc 10 For use, B is added to A.

The developing agents described in the present application may be used to form photographic images by development of exposed silver halide contained in the usual gelatin carrier or in carriers such as collodion, water-permeable cellulose ester or water-permeable synthetic resins. Our developing agents may be used with photographic films containing the coupler in the emulsion layer as described in Mannes and Godowsky U. S. Patent 2,304,940, granted December 15, 1942, or Jelly and Vittum- U. S. Patent 2,322,022, granted June 15, 1943.

It will be understood that the examples included herein are illustrative only and that our invention is to be taken as limited only by the scope of the appended claims.

We claim:

l. A developing solution for producing a colored photographic image comprising a silver halide developing agent having the formula:

where R, R, R" and R represent lower alkyl groups, and a compound which couples with the oxidation product of said developing agent to form a colored image upon photographic development.

3. A developing solution for producing a colored image comprising as the silver halide ded veloping agent a substantial amount of 4-amino- N-ethyl-N-(N-methyl-fl-methyl sulfonamidoethyD-m-phenetidine, and a compound which couples with the oxidation product of said developing agent upon development to form a colored image.

ARNOLD WEISSBERGER.

DUDLEY B. GLASS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,193,015 Weissberger Mar. 12, 1940 2,356,475 Schinzel Aug. 22, 1944 FOREIGN PATENTS Number Country Date 536,577 Great Britain May 20, 1941 

1. A DEVELOPING SOLUTION FOR PRODUCING A COLORED PHOTOGRAPHIC IMAGE COMPRISING A SILVER HALIDE DEVELOPING AGENT HAVING THE FORMULA: 